CN103764312B - Self-curing making molds is with adhesive composition and use the manufacture method of its casting mold - Google Patents
Self-curing making molds is with adhesive composition and use the manufacture method of its casting mold Download PDFInfo
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- CN103764312B CN103764312B CN201280042567.4A CN201280042567A CN103764312B CN 103764312 B CN103764312 B CN 103764312B CN 201280042567 A CN201280042567 A CN 201280042567A CN 103764312 B CN103764312 B CN 103764312B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/167—Mixtures of inorganic and organic binding agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/224—Furan polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A kind of self-curing making molds adhesive composition, it contains furane resins and ionic compound, described ionic compound contains the a kind of above anion being selected from bisulfite ion, sulfurous acid ion, pyrosulfurous acid ion, thiosulfuric acid ion, polythionic acid ion and hydrosulfurous acid ion, the content of described anion is 0.006～0.60 weight portion with respect to described furane resins active ingredient 100 weight portions, and described self-curing making molds with adhesive composition, the pH at 25 DEG C is below 6. Cation in above-mentioned ionic compound is preferably the metal ion in the element that is selected from the periodic table of chemical element the 1st family, the 2nd family and the 12nd family. In addition, the anion in above-mentioned ionic compound be preferably be selected from thiosulfuric acid ion, bisulfite ion and sulfurous acid ion more than a kind.
Description
Technical field
The present invention relates to self-curing making molds adhesive composition and use its casting moldManufacture method.
Background technology
As the casting mold for the manufacture of foundry goods, known self-curing casting mold, the casting mold that is heating and curing, gasSolidify casting mold etc. The self-curing casting mold being used at most obtains by the following method: by silica sandCombine etc. adding the self-curing making molds binding agent that contains furane resins etc. in fire resistance particleThing and the curing agent that contains phosphoric acid, organic sulfonic acid, sulfuric acid etc., they are mixing after, by gainedMixing sand is filled in the grand master patterns such as wooden mould, thereby obtains self-curing casting mold.
As above-mentioned furane resins, used furfuryl alcohol, furfuryl alcohol condensation polymer, furfuryl alcohol-urea formaldehyde resin,Furfuryl alcohol-formaldehyde resin, furfuryl alcohol-phenol-formaldehyde resin, other known modified furan resins etc.
On the other hand, in patent documentation 1,2, as the additive of adhesive composition, Asia is disclosedSulfate, thiosulfate plasma compound.
Following content is disclosed in patent documentation 1: for doing with fire resistance aggregate and curability binding agentFor main composition composition and curability binding agent are included in, in 1 molecule, to have more than 2 olefinic unsaturatedThe mold material that the multi-functional acrylic amide of group forms, its tachy steroling property of low temperature, crumbling property, canBy time aspect excellence, be particularly suitable as the casting mold material of the low-melting-point metals such as aluminium alloyMaterial. Above-mentioned curability binding agent is that to have the polymerism of the curing mechanism different from existing binding agent organicCompound, and can use the conducts such as metallic soap such as the such sulphite of sodium hydrogensulfite, aphthenic acids brillRedox series catalysts.
In patent documentation 2, disclose a kind of casting mold composition, it is characterized in that, it is that comprise canUtilize the acid acid cure of the potentiality curing agent of curing organic resin and this organic resin at normal temperaturesType resin combination, wherein, above-mentioned potentiality curing agent can utilize ozone to form three oxidations for being selected fromAt least one in the sulphur compound of sulphur. And, as potentiality curing agent, sulphite is disclosedThe aldehyde of class, bisulfite salt, pyrosulfurous acid salt, hyposulfite class, hyposulfite class addsBecome thing, thiosulfates etc.
Prior art document
Patent documentation
Patent documentation 1:WO90/02007 communique
Patent documentation 2: Japanese kokai publication sho 55-120445 communique
Summary of the invention
Invent problem to be solved
For the mold material of recording in above-mentioned patent documentation 1, due to redox series catalystsFor neutral or alkaline, thereby by the furane resins system that utilizes sour dehydration polycondensation reaction to be curedAdhesive composition cannot promote curing reaction. In addition, just in above-mentioned patent documentation 2, recordAcid cure type resin combination, although produce sulfur trioxide by continuous ozone supply,In the system of continuous supply that there is no ozone, cannot promote the curing reaction of curability organic resin.Like this, existing making molds with adhesive composition be not fully meet casting mold curing rate andThe composition of mould strength, expects the productive raising of casting mold.
The invention provides a kind of curing rate and mould strength and storage stability that can improve casting moldExcellent self-curing making molds is with adhesive composition and use the manufacturer of its casting moldMethod.
For the method for dealing with problems
Self-curing making molds of the present invention contains furane resins and ionization with adhesive compositionCompound, above-mentioned ionic compound contain be selected from bisulfite ion, sulfurous acid ion, pyrosulfurous acid fromIn son, thiosulfuric acid ion, polythionic acid ion and hydrosulfurous acid ion a kind above the moon fromSon, the content of above-mentioned anion is 0.006～0.60 weight with respect to above-mentioned furane resins 100 weight portionsPart, and described self-curing making molds with adhesive composition, the pH at 25 DEG C is below 6.
The manufacture method of casting mold of the present invention is to have to make the self-curing casting mold that comprises the invention described aboveThe casting mold of the operation of the mixture solidified of adhesive composition, fire resistance particle and curing agent for mouldingManufacture method.
The effect of invention
According to self-curing making molds adhesive composition of the present invention, owing to can improving casting moldCuring rate and mould strength, thereby can stably produce casting mold, and the productivity of casting mold becomesWell. In addition, self-curing making molds of the present invention is good with the storage stability of adhesive compositionGood.
Detailed description of the invention
Self-curing of the present invention for making molds adhesive composition (below also referred to as " binding agentComposition ") contain furane resins and ionic compound, above-mentioned ionic compound contains and is selected from bisulfiteIon, sulfurous acid ion, pyrosulfurous acid ion, thiosulfuric acid ion, polythionic acid ion and company two1 kind of above anion in sulfurous acid ion, the content of above-mentioned anion is set with respect to above-mentioned furansFat 100 weight portions are 0.006～0.60 weight portion, and pH is below 6 at 25 DEG C, described self-curingMaking molds plays and improves the curing rate of casting mold and the effect of mould strength with adhesive composition. ThoughThe reason that so plays such effect is also uncertain, but can think reason as described below.
, can think: what in the present invention, use contains bisulfite ion, sulfurous acid ion, Jiao YaThe anion such as sulfate ion, thiosulfuric acid ion, polythionic acid ion, hydrosulfurous acid ion fromIf sub-compound coexists with curing agent such as sulfuric acid, produce than the low acid of pKa of sulfuric acid etc., acid strengthUprise, promote thus to solidify.
Below, describe for adhesive composition of the present invention. Adhesive composition of the present inventionContain furane resins and ionic compound.
<ionic compound>
Ionic compound of the present invention is selected from bisulfite ion, sulfurous acid ion, burnt sulfurous for containingMore than a kind in acid ion, thiosulfuric acid ion, polythionic acid ion and hydrosulfurous acid ionThe ionic compound of anion.
The ionic compound that contains anion of the present invention is preferably to be added with the form of cationic saltBe added in adhesive composition. As bisulfite ionic compound, can use the acidity of sulfurous acidSalt, as sulfurous acid ion compound, can use the salt of sulfurous acid, as pyrosulfurous acid ionizationCompound, can use the salt of pyrosulfurous acid, as thiosulfuric acid ionic compound, can use sulfo-The salt of sulfuric acid, as polythionic acid ionic compound, can use the salt of tetrathionic acid, as connecting twoSulfurous acid ion compound, can use salt hydrosulfurous. From improve casting mold curing rate andImprove the viewpoint of mould strength and set out, as anion, preferably thiosulfuric acid ion, bisulfite fromSon and sulfurous acid ion, more preferably thiosulfuric acid ion and bisulfite ion, further preferred sulfo-Sulfate ion.
In the situation that using salt as ionic compound, as the cation in ionic compound,Can list metal cation. As slaine, can list 1 valency, divalent and metals more than 3 valencys.From improving the viewpoint of storage stability of adhesive composition, the preferably metal below divalent, moreThe preferably metal of 1 valency.
From improving the curing rate of casting mold and improving the viewpoint of mould strength, ionization of the present inventionCation in compound is preferably by the element that is selected from the periodic table of chemical element the 1st family, the 2nd family and the 12nd familyIn a kind of cation (metal ion) that above element forms, more preferably by being selected from chemical element week1 kind of cation that above element forms in the element of phase Biao 1 family and the 2nd family, further preferredBy the a kind of cation that above element forms being selected from the element of the periodic table of chemical element the 1st family. FromIdentical viewpoint is set out, preferred Na ion and K ion, more excellent in the periodic table of chemical element the 1st familySelect Na ion. From identical viewpoint, preferred Mg ion in the periodic table of chemical element the 2nd familyAnd Ca ion, preferred Zn ion in the periodic table of chemical element the 12nd family. The periodic table of chemical element the 1stAmong the element of family, the 2nd family and the 12nd family, from identical viewpoint, preferably Na ion, K fromSon, Mg ion, Ca ion and Zn ion, more preferably Na ion and K ion, further preferred NaIon.
As bisulfite ion (HSO3 -) the object lesson of salt, can list sodium hydrogensulfite,Potassium bisulfite, bisulfite lithium, magnesium bisulfite, calcium bisulfite, zine hydrosulfite etc.
As sulfurous acid ion (SO3 -) the object lesson of salt, can list sodium sulfite (anhydrideOr 7 hydrate), potassium sulfite, lithium sulfite, magnesium sulfite (6 hydrate), calcium sulfite (1/2 waterCompound), zinc sulfite (2 hydrate), barium sulfite, sulfurous acid bismuth, silver sulfite etc.
As pyrosulfurous acid ion (S2O5 -) the object lesson of salt, can list sodium pyrosulfite,Potassium metabisulfite, pyrosulfurous acid magnesium, pyrosulfurous acid calcium, pyrosulfurous acid zinc etc.
As thiosulfuric acid ion (S2O3 -) the object lesson of salt, can list sodium thiosulfate (nothingWater thing or 5 hydrates), potassium thiosulfate, barium hyposulfite (1 hydrate), magnesium thiosulfate (6 hydrationsThing), calcium thiosulfate, thiosulfuric acid zinc etc.
As polythionic acid ion (SXO6 -) the object lesson of salt, can list sodium tetrathionate (2Hydrate), potassium tetrathionate, tetrathionic acid magnesium, tetrathionic acid calcium, tetrathionic acid zinc etc.
As hydrosulfurous acid ion (S2O4 -) the object lesson of salt, can list hydrosulfurous acidSodium, potassium hyposulfite, magnesium hyposulfite, calcium hyposulfite, zinc dithionite etc.
From improving the curing rate and the viewpoint that improves mould strength, these ionic compounds of casting moldIn, be preferably sodium hydrogensulfite, potassium bisulfite, sodium sulfite, sodium thiosulfate, thiosulfuric acidPotassium, magnesium thiosulfate, calcium thiosulfate, sodium tetrathionate and sodium dithionite, more preferably sub-Niter cake, potassium bisulfite, sodium sulfite, sodium thiosulfate, potassium thiosulfate, thiosulfuric acidMagnesium and calcium thiosulfate, more preferably sodium thiosulfate, potassium thiosulfate, magnesium thiosulfate andCalcium thiosulfate, further sodium thiosulfate more preferably.
About the mensuration of the content of the anion in ionic compound, bisulfite ion, sulfurous acid fromDetermining of son, pyrosulfurous acid ion, thiosulfuric acid ion, polythionic acid ion and hydrosulfurous acid ionComponent analysis can be confirmed by ion chromatography method, elementary analysis. In addition, these saltAlkali metal etc. can carry out qualitative and quantitative analysis by ICP luminescence analysis.
As the mixed method of ionic compound, can list by furane resins and ionic compound, itsMethod that his composition mixes, the furane resins that contain in advance ionic compound are mixed with other compositionsMethod etc. As the method that contains in advance ionic compound in furane resins, can list syntheticBefore reaction in starting monomer hybrid ionic compound and carry out synthetic method, mixed in synthetic reactionClose the method for ionic compound and the method for synthetic rear hybrid ionic compound. In addition, all rightThe acid that contains this anion in mixing, after sulfurous acid, thiosulfuric acid, hydrosulfurous acid etc., carry outNeutralization, generates ionic compound in adhesive composition or in furane resins. From reducing additionThe viewpoint of error is set out, and preferably in the time manufacturing adhesive composition, mixes. In addition, from manufactureThe viewpoint of easiness is set out, and preferably ionic compound is dissolved in to solvent, mixes after making solution.From deliquescent viewpoint, solvent preferred water.
From improving the curing rate of casting mold and improving the viewpoint of mould strength, what the present invention relates toIn ionic compound, the content of anion with respect to furane resins 100 weight portions be 0.006 weight portion withUpper, be preferably 0.009 weight portion above, more preferably 0.02 weight portion above, more preferably 0.03More than weight portion. In addition, from the viewpoint of the storage stability of adhesive composition, anionContent is below 0.60 weight portion with respect to furane resins 100 weight portions. Further, from improving casting moldCuring rate and the viewpoint of mould strength set out, the content of anion is with respect to furane resins 100 weightsAmount part be 0.60 weight portion following, be preferably 0.50 weight portion following, more preferably 0.20 weight portion withUnder, more preferably below 0.10 weight portion. If comprehensively these viewpoints, with respect to furane resinsThe cooperation content of the anionic compound of the present invention of 100 weight portions is 0.006～0.60 weightPart, be preferably 0.009 weight portion～0.50 weight portion, 0.02～0.20 weight portion, further more preferablyBe preferably 0.03～0.10 weight portion. It should be noted that, furane resins are to remove the furan beyond moistureFurane resins (furane resins active ingredient) is benchmark.
From improving the curing rate of casting mold and improving the viewpoint of mould strength, the present invention relates to fromIn sub-compound, more than the content of the anion in adhesive composition is preferably 0.006 % by weight,More preferably 0.008 % by weight is above, more preferably 0.03 % by weight is above, further more preferablyBe more than 0.05 % by weight. In addition, from the viewpoint of the storage stability of adhesive composition, excellentElect as below 0.54 % by weight. Further, from improving the curing rate of casting mold and the viewpoint of mould strengthSet out, more preferably 0.50 % by weight is following, more preferably 0.40 % by weight is following, furtherMore preferably below 0.20 % by weight. If comprehensively these viewpoints, the present invention in adhesive compositionThe content of anion be preferably 0.006～0.54 % by weight, more preferably 0.008～0.50 % by weight, enterOne step is preferably 0.03～0.40 % by weight, further 0.05～0.20 % by weight more preferably.
From the raising of the storage stability of adhesive composition and the curing rate of casting mold and mould strengthViewpoint set out, the content of the ionic compound of the present invention in adhesive composition is preferably0.005～2.0 % by weight, 0.01～1.0 % by weight more preferably.
<furane resins>
As furane resins, can use known resin in the past, for example can use by be selected from furfuryl alcohol,In the condensation polymer of the condensation polymer of furfuryl alcohol condensation polymer, furfuryl alcohol and aldehydes and furfuryl alcohol and aldehydes and urea 1The resin that kind forms, by the condensation polymer and the chaff that are selected from furfuryl alcohol, furfuryl alcohol condensation polymer, furfuryl alcohol and aldehydesThe resin that mixture of more than two kinds in the condensation polymer of alcohol and aldehydes and urea forms. In addition, alsoCan use by the condensation polymer and furfuryl alcohol and the aldehydes that are selected from furfuryl alcohol, furfuryl alcohol condensation polymer, furfuryl alcohol and aldehydesThe resin that forms with the co-condensation polymer of more than two kinds in the condensation polymer of urea, by being selected from furfuryl alcohol, chaffIn the condensation polymer of the condensation polymer of alcohol condensation polymer, furfuryl alcohol and aldehydes and furfuryl alcohol and aldehydes and urea a kindThe resin forming with the mixture of above-mentioned co-condensation polymer above. In addition, can also comprise by being selected from phenolIn the condensation polymer of condensation polymer, melamine and the aldehydes of class and aldehydes and the condensation polymer of urea and aldehydes 1Plant the material forming, and then the tree that can also use above-mentioned furane resins and their copolycondensations to formFat.
As above-mentioned aldehydes, can list formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, furfural, to benzeneDicarbaldehyde etc., can use in them more than a kind. From improving the viewpoint of mould strength, excellentChoosing is used formaldehyde, and the viewpoint of the formaldehyde generation during from minimizing moulding, is preferably used furfural, rightPhthalaldehyde.
As above-mentioned phenols, can list phenol, cresols, resorcinol, bisphenol-A, bisphenol-c,Bis-phenol E, Bisphenol F etc., can use in them more than a kind.
From improving the viewpoint of mould strength, at 25 DEG C the pH of furane resins be preferably be less than 7,More preferably below 6, more preferably below 5.5, be further preferably below 5, from preservingThe viewpoint of stability is set out, be preferably more than 1.9, more preferably more than 2.5, more preferably 3Above. If comprehensively these viewpoints, at 25 DEG C, the pH of furane resins is preferably 1.9～6, more preferablyBe 2.5～5.5, more preferably 3～5. Acid furane resins are preferably and use acidic catalyst to enterThe synthetic resin forming of row.
The acidic catalyst using when for furane resins of the present invention synthetic, from improving castingThe viewpoint of the curing rate of type and raising mould strength is set out, and preferably uses the acidity below pKa5.0 to urgeAgent.
As above-mentioned acidic catalyst, can use sulfuric acid (pKa:1.99), phosphoric acid (pKa:2.1) etc.Inorganic acid, benzene sulfonic acid (pKa:-2.5), p-methyl benzenesulfonic acid (pKa:-2.8), xylene monosulfonic acid (pKa:-2.6), the sulfonic acid such as Loprazolam (pKa:-2.0), tartaric acid (pKa:3.95), citric acid (pKa:2.87),Malic acid (pKa:3.24), glycolic (pKa:3.63), lactic acid (pKa:3.66), benzoic acid (pKa:4.20), the organic carboxyl acid such as formic acid (pKa:3.55). From improving the curing rate of casting mold and improving casting moldThe viewpoint of intensity is set out, preferably benzoic acid and formic acid. From improving the curing rate of casting mold and improving casting moldThe viewpoint of the security when viewpoint of intensity and manufacture is set out, and these acidic catalysts are preferablyPKa1.9～5.0, pKa3.0～4.5 more preferably.
The furane resins of gained can directly be used with acid state, also can enter as requiredRow neutralization. Carry out after the neutralization of furane resins, again become in acid situation, can addThe carboxylic acid such as glycolic, benzoic acid is to reach the pH of regulation.
In the time manufacturing furane resins, from improving the intensity of casting mold and the viewpoint of shortening manufacturing time,The mol ratio of monomer and acidic catalyst is preferably whole monomers: acidic catalyst=1: 0.0001～1:1.0, more preferably 1: 0.0005～1: 0.1, more preferably 1: 0.001～1: 0.05.
As above-mentioned monomer, can use furfuryl alcohol, urea, above-mentioned aldehydes, above-mentioned phenols, they rubYou can suitably adjust by ratio.
In the time manufacturing the condensation polymer of furfuryl alcohol, aldehydes and urea, from improving the viewpoint of mould strength,Preferably, with respect to 1 mole of furfuryl alcohol, use 0.05～3 mole of aldehydes, 0.03～1.5 mole, urea. From identicalViewpoint set out, as aldehydes, preferably formaldehyde.
From improving the viewpoint of mould strength, the nitrogen content in furane resins is preferably 0.8～6.0 weightAmount %, more preferably 1.8～5.0 % by weight, 2.0～4.0 % by weight more preferably.
The viewpoint of the easy degree from processing, the free furfuryl alcohol in furane resins is with moisture contentComposition benchmark meter, be preferably 20～98 % by weight, 20～95 % by weight, further excellent more preferablyElect 20～80 % by weight as, be further preferably 30～75 % by weight, in moisture described later beIn the situation of 10～20 % by weight, more preferably 35～85 % by weight, further more preferably 35～65% by weight.
From improving the viewpoint of mould strength, the content of the furfuryl alcohol in adhesive composition is preferably 20% by weight is above, more preferably 45 % by weight above, more preferably 60 % by weight above, enter oneStep is more preferably more than 70 % by weight. From reducing the viewpoint of incendivity, in adhesive compositionThe content of furfuryl alcohol is preferably that 98 % by weight are following, more preferably 95 % by weight are following, more preferablyBelow 90 % by weight. In addition, from improving the viewpoint of mould strength and the viewpoint of minimizing incendivity,The content of the furfuryl alcohol in adhesive composition is preferably 20～98 % by weight, 45～95 weights more preferablyAmount %, more preferably 60～90 % by weight, further 70～90 % by weight more preferably.
Never damage the viewpoint of the mobility of mixing sand and set out, the viscosity of furane resins is preferably at 25 DEG CBe 5.5～50mPas.
In the case of the various condensation polymers such as the condensation polymer of synthetic furfuryl alcohol and aldehydes, due to the use aqueous solutionThe raw material of shape or generate condensation water, thereby conventionally to obtain polycondensation with the form of the mixture of moistureThing, by such condensation polymer when the furane resins, do not need from these in building-up processMoisture is removed. , the viewpoint of the easy degree in the convenience from manufacturing and processing, furansResin can contain moisture. From improving the viewpoint of curing rate of casting mold, the moisture of furane resinsContent is preferably that 30 % by weight are following, following, 20 % by weight more preferably of 25 % by weight more preferablyBelow. Can not produce incendivity and make furane resins not be equivalent to the viewpoint of danger from furane resinsSet out, the moisture of furane resins is preferably 3.0 % by weight and above, is more preferably greater than 6.0 weightsAmount %, more preferably more than 10 % by weight. If comprehensively these viewpoints, the moisture of furane resinsContent is preferably 3.0～30 % by weight, is more preferably greater than 6.0～30 % by weight, more preferably largeIn 6.0～25 % by weight, further 10～20 % by weight more preferably. It should be noted that, in the present invention,In the time of the weight relationships of other compounds of explanation and furane resins, to remove the furane resins beyond moisture(furane resins active ingredient) is benchmark.
From fully demonstrating the viewpoint of mould strength, the furane resins (furans in adhesive compositionResin active ingredient) content be preferably 50 % by weight above, more preferably 55 % by weight above, enter oneMore than step is preferably 60 % by weight, further more preferably more than 70 % by weight. From reducing incendivityViewpoint is set out, and the content of the furane resins (furane resins active ingredient) in adhesive composition is preferably99 % by weight are following, more preferably 95 % by weight following, more preferably below 90 % by weight. SeparatelyOutward, from fully demonstrating the viewpoint of mould strength and the viewpoint of minimizing incendivity, adhesive compositionIn the content of furane resins (furane resins active ingredient) be preferably 50～99 % by weight, more preferably55～95 % by weight, more preferably 60～90 % by weight, further 70～90 % by weight more preferably.
Adhesive composition of the present invention can also contain curing accelerator, water, other additives.
<curing accelerator>
From prevent casting mold cracking viewpoint and improve the viewpoint of final mould strength, thisIn bright adhesive composition, can comprise curing accelerator. As curing accelerator, from improvingThe viewpoint of whole mould strength is set out, and is preferably and is selected from the compound shown in following general formula (1) (below,Be called curing accelerator (1)), in phenol derivatives and aromatic series dialdehyde more than a kind.
(in formula (1), X1And X2Represent respectively hydrogen atom, CH3Or C2H5In any. )
As curing accelerator (1), can list the two hydroxymethylfurans, 2 of 2,5-, 5-bi-methoxy firstBase furans, 2, the two ethoxyl methyl furans of 5-, 2-methylol-5-methoxy furans, 2-hydroxyl firstBase-5-ethoxyl methyl furans, 2-methoxy-5-ethoxyl methyl furans. Especially, from improvingThe viewpoint of final mould strength is set out, and preferably uses the two hydroxymethylfurans of 2,5-. Promote from solidifyingThe deliquescent viewpoint of agent (1) in furane resins and the viewpoint that improves final mould strength are set out,The content of the curing accelerator (1) in adhesive composition is preferably 0.5～53 % by weight, more preferably1.8～50 % by weight, more preferably 2.5～40 % by weight, further 3.0～30 % by weight more preferably.
As phenol derivatives, can list resorcinol, cresols, quinhydrones, phloroglucin, methyleneBase bis-phenol etc. Especially,, from improving the viewpoint of final mould strength, be preferably resorcinol.Deliquescent viewpoint from phenol derivatives furane resins and the sight that improves final mould strengthPoint sets out, and the content of the above-mentioned phenol derivatives in adhesive composition is preferably 1～25 % by weight, moreBe preferably 2～15 % by weight, 3～10 % by weight more preferably. Especially, using resorcinolIn situation, the deliquescent viewpoint from resorcinol furane resins and improve final mould strengthViewpoint set out, the content of the resorcinol in adhesive composition is preferably 1～10 % by weight, more excellentElect 2～7 % by weight, 3～6 % by weight more preferably as.
As aromatic series dialdehyde, can list terephthalaldehyde, OPA and m-terephthal aldehyde etc.,And their derivative etc. Their derivative refers to, in 2 first that have as basic frameworkOn the aromatic rings of the aromatic compound of acyl group, there is the substituent compounds such as alkyl etc. From preventing castingThe viewpoint of the cracking of type is set out, and is preferably the derivative of terephthalaldehyde and terephthalaldehyde, more preferablyFor terephthalaldehyde. From making aromatic series dialdehyde fully be dissolved in the viewpoint of furane resins and suppress aromatic seriesThe viewpoint of the stink of dialdehyde self is set out, and the content of the aromatic series dialdehyde in adhesive composition is preferably0.1～15 % by weight, more preferably 0.5～10 % by weight, 1～5 % by weight more preferably.
<moisture>
In adhesive composition of the present invention, can also comprise moisture. Furane resins are owing to as mentioned above canTo contain moisture, thereby adhesive composition of the present invention also can contain the moisture that comes from it. FromThis viewpoint is set out, more than the moisture in adhesive composition is preferably 3.0 % by weight. In addition,For adhesive composition being adjusted into object of easy to handle viscosity etc., can also add moisture.But, if moisture is excessive, the possibility that exists the curing reaction of furane resins to be hindered, thereby stickyMoisture in knot agent composition be preferably 30.0 % by weight following, more preferably 25.0 % by weight withUnder, more preferably below 20.0 % by weight. Do not produce incendivity and make to glue from adhesive compositionKnot agent composition is not equivalent to the viewpoint of danger and sets out, and the moisture in adhesive composition is preferredFor be greater than 6.0 % by weight, more preferably 10 % by weight above, more preferably 15 % by weight above,More than being further preferably 20 % by weight. If comprehensively these viewpoints, the water in adhesive compositionPoint content is preferably that 3.0 % by weight are above and 30.0 % by weight are following, be more preferably greater than 6.0 % by weight andBelow 30.0 % by weight, be more preferably greater than 6.0 % by weight and below 25.0 % by weight, moreMore preferably 10.0～25.0 % by weight, further 10.0～20.0 % by weight more preferably. From improvingThe viewpoint of mould strength is set out, and is preferably 3～15 % by weight, 3～10 % by weight more preferably.
<other additives>
In addition, from improving the viewpoint of mould strength, all right in adhesive composition of the present inventionComprise the additives such as silane coupler. As silane coupler, can use N-β-(amino-ethyl)-γ-Aminopropyl methyl dimethoxysilane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane,The ammonia such as N-β-(amino-ethyl)-γ aminopropyltriethoxy silane, 3-TSL 8330Base silane, 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxysilane,The epoxies such as 3-epoxypropoxy methyldiethoxysilane, 3-epoxypropoxy triethoxysilaneBase silane, ureido silane, hydrosulphonyl silane, thioether silane, methacryloxypropyl silane, acryloylTMOS etc. Be preferably amino silane, epoxy radicals silicone hydride, ureido silane. From improving mould strengthViewpoint set out, the content of silane coupler in adhesive composition be preferably 0.01～0.5 % by weight,More preferably 0.05～0.3 % by weight.
From improving the viewpoint of mould strength, the nitrogen content in adhesive composition is preferably0.6～5.0 % by weight, more preferably 1.5～4.2 % by weight, 1.6～3.4 % by weight more preferably.
From improving the viewpoint of mould strength, at 25 DEG C the pH of adhesive composition be below 6,Be preferably below 5.8, more preferably below 5.6, from the viewpoint of storage stability, be preferably 2Above, more preferably more than 3, more preferably more than 4. If comprehensively these viewpoints, at 25 DEG CThe pH of lower furane resins is preferably 2～6, more preferably 3～5.8, more preferably 4～5.6. BondingThe pH of agent composition can use the carboxylic acid such as inorganic acid or glycolic, benzoic acid, the hydrogen-oxygens such as sulfuric acidChange the alkali such as sodium and be adjusted to the pH of regulation. It should be noted that, adhesive composition of the present invention orThe pH of furane resins is values as described below: at 25 DEG C to respect to adhesive composition or furansResin carry out mixing water with weight ratio 50/50 and stir after material measure and the value that obtains.
Adhesive composition of the present invention is suitable for having by self-curing making molds binding agent groupCompound, fire resistance particle and acid curing agent mix and acquisition self-curing making molds compositionOperation and make the manufacture method of the casting mold of the operation of this mixture solidified. , casting of the present inventionThe manufacture method of type is to use the adhesive composition of the invention described above as self-curing making moldsBy the manufacture method of the casting mold of adhesive composition.
In the manufacture method of casting mold of the present invention, can directly utilize the manufacture method of existing casting moldTechnique is manufactured casting mold. For example, in fire resistance particle, add the invention described above adhesive composition,The curing curing agent with making this adhesive composition, utilizes intermittent mixer, continuous mixer etc. by itMixing, can obtain thus said mixture (mixing sand). In the manufacture method of casting mold of the present invention,From improving the viewpoint of mould strength, preferably in fire resistance particle, add after above-mentioned curing agent, addAdd adhesive composition of the present invention.
As fire resistance particle, can use silica sand, chromite sand, zircon sand, olivine sand, oxidationAloxite, Mo Laisha, syntheticly do not carry out the existing known materials such as sand, in addition, can also use useMaterial or the reclaimed sand after treatment etc. of regenerating that complete fire resistance particle obtains after reclaiming.
As compound contained in curing agent, can use a kind of above xylene monosulfonic acid that comprisesThe sulfonic acid such as (particularly meta-xylene sulfonic acid), toluenesulfonic acid (particularly p-methyl benzenesulfonic acid), LoprazolamThe acidic aqueous solutions of phosphoric acid based compound, the sulfuric acid etc. such as based compound, phosphoric acid, acid phosphoric acid ester etc. are existingThere is known material. Further, in curing agent, can contain and be selected from alcohols, ether alcohol class and ester class1 kind of above solvent, carboxylic acids. From realizing the viewpoint of raising of final mould strength,Preferred alcohols, ether alcohol class, more preferably ether alcohol class in the middle of these. In addition, if contain above-mentioned solvent, carboxylicAcids, because the amount of moisture in curing agent reduces, thereby further improves final mould strength.From improving the viewpoint of final mould strength, in the curing agent of above-mentioned solvent, above-mentioned carboxylic acidsContent is preferably 5～50 % by weight, 10～40 % by weight more preferably. In addition, from reducing curing agentThe viewpoint of viscosity is set out, and contains methyl alcohol, ethanol in preferred consolidation agent.
From realizing the viewpoint of raising of mould strength, as above-mentioned alcohols, be preferably propyl alcohol, fourthAlcohol, amylalcohol, hexanol, enanthol, octanol, benzylalcohol, as ether alcohol class, be preferably ethylene glycol monoethyl ether,Ethylene glycol monobutyl ether, ethylene glycol ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diglycol monotertiaryHexyl ether, diglycol monotertiary phenylate, ethyleneglycol monophenylether, as ester class, be preferably butyl acetate, benzene firstAcid butyl ester, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetic acid esters. From improving final casting moldThe viewpoint of intensity and minimizing stink is set out, and as carboxylic acids, is preferably the carboxylic acid with hydroxyl, more excellentElect lactic acid, citric acid, malic acid as.
In mixing sand, the ratio of fire resistance particle, adhesive composition and curing agent can suitably be set,With respect to fire resistance particle 100 weight portions, adhesive composition is preferably 0.5～1.5 weight portion, solidifiesAgent is preferably the scope of 0.07～1 weight portion. If such ratio, easily obtains intensity sufficientCasting mold. Further, from reducing as possible the viewpoint of amount of moisture contained casting mold and utilizing mixerThe viewpoint of mixing efficiency is set out, with respect to furane resins 100 weight portions in adhesive composition, GuThe addition of agent is preferably 10～40 weight portions, 15～35 weight portions more preferably.
Self-curing making molds of the present invention contains above-mentioned self-curing making molds with composition to be usedThe curing agent of adhesive composition, above-mentioned fire resistance particle and above-mentioned acidity. Self-curing of the present inventionMaking molds preferably with respect to above-mentioned fire resistance particle 100 weight portions, contains above-mentioned from solid with compositionAdhesive composition 0.5～1.5 weight portion and above-mentioned curing agent 0.07～1 weight portion for voltinism making molds.It should be noted that, the preferred configuration of the curing agent of fire resistance particle, acidity etc. is described above.
Self-curing making molds of the present invention is suitable for Casting mold manufacturing with adhesive composition.
Composition of the present invention is as described below:
<1>a self-curing making molds adhesive composition, it contains furane resins and ionCompound, above-mentioned ionic compound contains and is selected from bisulfite ion, sulfurous acid ion, pyrosulfurous acid1 kind of above the moon in ion, thiosulfuric acid ion, polythionic acid ion and hydrosulfurous acid ionIon, with respect to above-mentioned furane resins active ingredient 100 weight portions, the content of above-mentioned anion is0.006～0.60 weight portion, and at 25 DEG C, pH is below 6.
The present invention is preferred following composition or manufacture method or purposes also.
<2>according to above-mentioned<1>described self-curing making molds adhesive composition, wherein,Cation in above-mentioned ionic compound is served as reasons and is selected from the periodic table of chemical element the 1st family, the 2nd family and the 12nd1 kind of metal ion that above element forms in the element of family, is preferably by being selected from chemical element week1 kind of metal ion that above element forms in the element of phase Biao 1 family and the 2nd family, more preferablyBy the a kind of metal ion that above element forms being selected from the element of the periodic table of chemical element the 1st family.
<3>according to above-mentioned<1>or<2>described self-curing making molds adhesive composition, itsIn, the anion in above-mentioned ionic compound is for being selected from thiosulfuric acid ion, bisulfite ion and AsiaIn sulfate ion more than a kind, be preferably and be selected from 1 in thiosulfuric acid ion and bisulfite ionMore than kind, more preferably thiosulfuric acid ion.
<4>according to above-mentioned<1>～<3>in self-curing making molds binding agent group described in any oneCompound, wherein, the cation of above-mentioned ionic compound for be selected from Na ion, K ion, Mg ion,In Ca ion and Zn ion more than a kind, be preferably Na ion, K ion, more preferably Na ion.
<5>according to above-mentioned<1>～<4>in self-curing making molds binding agent group described in any oneCompound, wherein, above-mentioned ionic compound for be selected from sodium hydrogensulfite, potassium bisulfite, sodium sulfite,Sodium thiosulfate, potassium thiosulfate, magnesium thiosulfate, calcium thiosulfate, sodium tetrathionate and company twoIn sodium sulfite more than a kind, be preferably be selected from sodium hydrogensulfite, potassium bisulfite, sodium sulfite,In sodium thiosulfate, potassium thiosulfate, magnesium thiosulfate and calcium thiosulfate more than a kind, more excellentElect as a kind of being selected from sodium thiosulfate, potassium thiosulfate, magnesium thiosulfate and calcium thiosulfate withOn.
<6>according to above-mentioned<1>～<5>in self-curing making molds binding agent group described in any oneCompound, wherein, with respect to above-mentioned furane resins active ingredient 100 weight portions, the containing of above-mentioned anionAmount is more than 0.009 weight portion, more than being preferably 0.02 weight portion, and more preferably more than 0.03 weight portion,In addition, the content of above-mentioned anion is below 0.50 weight portion, is preferably below 0.20 weight portion, moreBe preferably below 0.10 weight portion.
<7>according to above-mentioned<1>～<6>in self-curing making molds binding agent group described in any oneCompound, wherein, the content of the anion of above-mentioned ionic compound is 0.006 in adhesive compositionMore than % by weight, more than being preferably 0.008 % by weight, more preferably more than 0.03 % by weight, furtherMore than being preferably 0.05 % by weight, in addition, the content of the anion of above-mentioned ionic compound is at binding agentIn composition, be below 0.54 % by weight, be preferably below 0.50 % by weight, more preferably 0.40 % by weightBelow, more preferably below 0.20 % by weight.
<8>according to above-mentioned<1>～<7>in self-curing making molds binding agent group described in any oneCompound, wherein, in adhesive composition the content of above-mentioned ionic compound be 0.005 % by weight withUpper, more than being preferably 0.01 % by weight, in addition, above-mentioned ionic compound in adhesive compositionContent is below 2.0 % by weight, is preferably below 1.0 % by weight.
<9>according to above-mentioned<1>～<8>in self-curing making molds binding agent group described in any oneCompound, wherein, at 25 DEG C, the pH of above-mentioned furane resins, for being less than 7, is preferably below 6, more excellentElect as below 5.5, more preferably below 5, in addition, the pH of above-mentioned furane resins at 25 DEG CBe more than 1.9, be preferably more than 2.5, more preferably more than 3.
<10>according to above-mentioned<1>～<9>in self-curing making molds binding agent described in any oneComposition, wherein, above-mentioned furane resins for use pKa5.0 following, be preferably pKa1.9～5.0, moreBe preferably the resin that the acidic catalyst of pKa3.0～4.5 is synthesized into.
<11>according to above-mentioned<1>～<10>in self-curing making molds binding agent described in any oneComposition, wherein, above-mentioned acidic catalyst for be selected from sulfuric acid, phosphoric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid,Xylene monosulfonic acid, Loprazolam, tartaric acid, citric acid, malic acid, glycolic, lactic acid, benzene firstIn acid and formic acid more than a kind, be preferably be selected from benzoic acid and formic acid more than a kind.
<12>according to above-mentioned<1>～<11>in self-curing making molds binding agent described in any oneComposition, wherein, the content of the free furfuryl alcohol in above-mentioned furane resins is 20～98 % by weight, preferablyBe 20～95 % by weight, more preferably 20～80 % by weight, more preferably 30～75 % by weight, moreMore preferably 35～65 % by weight.
<13>according to above-mentioned<1>～<12>in self-curing making molds binding agent described in any oneComposition, wherein, the furfuryl alcohol content in adhesive composition is more than 20 % by weight, is preferably 45More than % by weight, more preferably more than 60 % by weight, more preferably more than 70 % by weight, in addition,Furfuryl alcohol content in adhesive composition is below 98 % by weight, is preferably below 95 % by weight, more excellentElect as below 90 % by weight.
<14>according to above-mentioned<1>～<13>in casting mold in solidity adhesive composition described in any oneMoulding adhesive composition, wherein, the moisture in above-mentioned furane resins is below 30 % by weight,Be preferably below 25 % by weight, more preferably below 20 % by weight, in addition, the moisture in furane resinsContent is more than 3.0 % by weight, is preferably more than 6.0 % by weight, more preferably more than 10 % by weight.
<15>according to above-mentioned<1>～<14>in self-curing making molds binding agent described in any oneComposition, wherein, the content of above-mentioned furane resins (furane resins active ingredient) is more than 50 % by weight,More than being preferably 55 % by weight, more preferably more than 60 % by weight, more preferably 70 % by weight withUpper, in addition, the content of above-mentioned furane resins (furane resins active ingredient) is below 99 % by weight, excellentElect as below 95 % by weight, more preferably below 90 % by weight.
<16>according to above-mentioned<1>～<15>in self-curing making molds binding agent described in any oneComposition, wherein, the moisture in adhesive composition is below 30.0 % by weight, is preferably 25.0Below % by weight, more preferably, below 20.0 % by weight, in addition, the moisture in adhesive composition containsAmount, for being greater than 6.0 % by weight, more than being preferably 10 % by weight, more preferably more than 15 % by weight, enters oneMore than step is preferably 20 % by weight.
<17>according to above-mentioned<1>～<16>in self-curing making molds binding agent described in any oneComposition, wherein, at 25 DEG C, the pH of adhesive composition is below 5.8, be preferably below 5.6,In addition, at 25 DEG C, the pH of adhesive composition is more than 2, be preferably more than 3, more preferably 4 withOn.
<18>according to above-mentioned<1>～<17>in self-curing making molds binding agent described in any oneComposition, wherein, adhesive composition also contains and is selected from the two hydroxymethylfurans, 2 of 2,5-, the two first of 5-Oxygen ylmethyl furans, 2, the two ethoxyl methyl furans of 5-, 2-methylol-5-methoxy furans,In 2-methylol-5-ethoxyl methyl furans and 2-methoxy-5-ethoxyl methyl furans a kind withUpper, preferably contain the two hydroxymethylfurans of 2,5-.
<19>a self-curing making molds composition, it contains above-mentioned<1>～<18>in arbitrarySelf-curing described in is adhesive composition, fire resistance particle and acid solidifying for making moldsAgent, preferably with respect to fire resistance particle 100 weight portions, contains above-mentioned self-curing making molds with stickyKnot agent composition 0.5～1.5 weight portion and above-mentioned curing agent 0.07～1 weight portion.
<20>above-mentioned<1>～<18>in self-curing making molds described in any one combine with binding agentThe purposes for Casting mold manufacturing of thing.
<21>manufacture method for casting mold, it has following operation:
By above-mentioned<1>～<18>in self-curing making molds described in any one combine with binding agentThing, fire resistance particle and acid curing agent mix, acquisition self-curing making molds use compositionOperation, and make the operation of this mixture solidified.
Embodiment
Below, describe for particular instantiation embodiments of the invention etc.
(embodiment 1～26 and comparative example 1～17)
Use furane resins A and ionic compound, the composition shown in mixture table 1～4, prepares binding agentComposition, then prepares mixing sand according to following preparation method, for the mixing sand of gained, according underCommentary valency method evaluation the mould strength after 1 hour and after 24 hours. Table 1～4 illustrate result.It should be noted that, furane resins A contained in the adhesive composition of the composition shown in table 1～4 isUse the resin that obtains as acidic catalyst of benzoic acid (pKa:4.20), the monomer when synthetic withThe mol ratio of acidic catalyst is whole monomers: acidic catalyst=1: 0.01. As monomer, useFurfuryl alcohol, formaldehyde and urea, and the mol ratio of furfuryl alcohol/formaldehyde/urea is 2.5/3.6/1. Embodiment 1～26And in comparative example 1～17, add silane according to the mode that becomes 0.1 % by weight in adhesive compositionCoupling agent (N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane). It should be noted that,In comparative example 1, add as pH adjusting agent in the mode that becomes 1.4 % by weight in adhesive composition48% caustic soda. The pH of adhesive composition or furane resins is values as described below: at 25 DEG CUnder for carrying out mixing water and stir in weight ratio 50/50 with respect to adhesive composition or furane resinsMaterial after mixing measure and value.
It should be noted that, the proterties of furane resins A is as described below.
The proterties of<furane resins A>
Free furfuryl alcohol=60 % by weight
Furfuryl alcohol-urea formaldehyde resin=24.0 % by weight
Nitrogen content=2.5 % by weight
Moisture=16 % by weight
pH＝4.5(25℃)
Viscosity=38mPas/at25 DEG C (condition determination: Brookfield viscometer rotor No360rpm)
(embodiment 27～34 and comparative example 18～22)
Use furane resins B, C, D, the application's ionic compound, 2, two (methylol) furans of 5-Mutter, silane coupler (N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane), preparationThe adhesive composition of the composition shown in table 5～7, then similarly to Example 1, obtains mixing sand,Measure the mould strength after 1 hour and after 24 hours. Table 5～7 illustrate result. It should be noted that,In the adhesive composition of the composition shown in table 5～7, contained furane resins B, C, D is by following instituteThe resin that the furane resins U showing is obtained by mixing according to the ratio shown in following and chaff alcohol and water. Make formaldehydeIn water, react with the NaOH as base catalyst with urea. The integral molar quantity of formaldehyde and ureaWith the ratio of the mole of base catalyst be 1: 0.0002. Further add furfuryl alcohol, utilize formic acid (pKa:3.55) pH is adjusted to 4.5, after reacting, being heated to interior temperature is 150 DEG C, under normal pressure, carries outConcentrated, obtain furane resins U (ureaformaldehyde modified furan resin). Monomer and acidic catalyst when syntheticThe mol ratio of agent is whole monomers: acidic catalyst=1: 0.0036. As monomer, use furfuryl alcohol,Formaldehyde and urea, and the mol ratio of furfuryl alcohol/formaldehyde/urea is 2.6/2.1/1.
Coordinate furane resins U30.7g, furfuryl alcohol 52.3g and water 17.0g, obtain furane resins B. WithSample ground coordinates furane resins U44.9g, furfuryl alcohol 28.5g and water 26.6g, obtains furane resins C.Further, coordinate furane resins U9.7g, furfuryl alcohol 87.3g and water 3.0g, obtain furane resins D.
It should be noted that, in embodiment 29, embodiment 30 and comparative example 18, use 48% caustic sodaAs pH adjusting agent, being adjusted to pH is the pH shown in table 5. Adhesive composition or furane resinsPH is value as described below: at 25 DEG C for respect to adhesive composition or furane resins withWeight ratio 50/50 come mixing water and stir after material measure and value.
It should be noted that, the proterties of furane resins B, C, D is as described below.
The proterties of<furane resins B>
Free furfuryl alcohol=63.4 % by weight
Furfuryl alcohol-urea formaldehyde resin=18.8 % by weight
Nitrogen content=2.6 % by weight
Moisture=17.8 % by weight
pH＝4.5(25℃)
Viscosity=9.9mPas/at25 DEG C (condition determination: Brookfield viscometer rotor No360rpm)
The proterties of<furane resins C>
Free furfuryl alcohol=44.7 % by weight
Furfuryl alcohol-urea formaldehyde resin=27.5 % by weight
Nitrogen content=3.8 % by weight
Moisture=27.8 % by weight
pH＝4.6(25℃)
Viscosity=14.1mpas/at25 DEG C (condition determination: Brookfield viscometer rotor No360rpm)
The proterties of<furane resins D>
Free furfuryl alcohol=90.8 % by weight
Furfuryl alcohol-urea formaldehyde resin=5.9 % by weight
Nitrogen content=0.8 % by weight
Moisture=3.3 % by weight
pH＝4.5(25℃)
Viscosity=6.5mPas/at25 DEG C (condition determination: Brookfield viscometer rotor No360rpm)
The preparation method of<mixing sand>
Under 25 DEG C, the atmosphere of 55%RH, with respect to Fremantle fresh sand (mountains and rivers Industry Co., LtdSystem) 2000 weight portions, adding xylene monosulfonic acid/sulfuric acid is the curing agent (Kao processed of Hua Wang Quaker companyLightner curing agent US-3 and Hua Wang Quaker company KaoLightner curing agent processed C-21'sThe 55.4 % by weight aqueous solution of mixture (weight ratio is US-3/C-21=12/28)) 8.0 weight portions, thenAdd previously prepared above-mentioned adhesive composition 20.0 weight portions, they are mixed, obtain mixing sand.
The evaluation method of the mould strength after<1 hour and after 24 hours>
Under 25 DEG C, the atmosphere of 55%RH, above-mentioned mixing sand after just mixing is filled into diameterIn the test specimen frame of the cylindrical shape of 50mm, high 50mm. Then, 25 DEG C, the atmosphere of 55%RHLower placement, measures the compressive strength of filling after 1 hour, sets it as " mould strength after 1 hour ".Then, during through 5 hours, carry out punch die, further under 25 DEG C, the atmosphere of 55%RH, after punch die, putPut 19 hours, then measure compressive strength, set it as " mould strengths after 24 hours ". NeedBright, according to the method based on JISZ2604-1976, measure compressive strength.
The dissolubility of<additive at 35 DEG C after 2 months>
For the dissolubility of the additive of the adhesive composition shown in confirmation form 2～4, moved and changed toIn transparent container, at 35 DEG C, place 2 months. Table 2～4 illustrate confirms the molten of each additiveThe result of solution property.
[table 1]
As shown in table 1, embodiment 1～14 is with respect to comparative example 1～8, after 1 hour and after 24 hoursMould strength higher, thereby known casting mold productivity improves.[table 2]
As shown in table 2, embodiment 15,16,1,17,18 is with respect to comparative example 9,10,11,Mould strength after 1 hour and after 24 hours is higher, thereby known casting mold productivity improves. RightIn embodiment 15,16,1,17,18, the dissolubility of known ionic compound is also no problem.On the other hand, an ionic compound part for comparative example 10,11 is not dissolved.
[table 3]
As shown in table 3, embodiment 19,20,9,21,22 is with respect to comparative example 12,13,14,Mould strength after 1 hour and after 24 hours is higher, thereby known casting mold productivity improves. RightIn embodiment 19,20,9,21,22, the dissolubility of known ionic compound is also no problem.On the other hand, an ionic compound part for comparative example 13,14 is not dissolved.
[table 4]
As shown in table 4, embodiment 23,24,3,25,26 is with respect to comparative example 15,16,17,Mould strength after 1 hour and after 24 hours is higher, thereby known casting mold productivity improves. RightIn embodiment 23,24,3,25,26, the dissolubility of known ionic compound is also no problem.On the other hand, an ionic compound part for comparative example 16,17 is not dissolved.
[table 5]
As shown in table 5, embodiment 27～30 is with respect to comparative example 18～20, after 1 hour and 24 littleTime after mould strength higher, thereby known casting mold productivity improves.[table 6]
As shown in table 6, embodiment 31,32 is with respect to comparative example after 21,1 hours and after 24 hoursMould strength higher, thereby known casting mold productivity improves.
[table 7]
As shown in table 7, embodiment 33,34 is with respect to comparative example after 22,1 hours and after 24 hoursMould strength higher, thereby known casting mold productivity improves.
Claims (21)
1. a self-curing making molds adhesive composition, it contains furane resins and ionizationCompound, described ionic compound contain be selected from bisulfite ion, sulfurous acid ion, pyrosulfurous acid fromIn son, thiosulfuric acid ion, polythionic acid ion and hydrosulfurous acid ion a kind above the moon fromSon, the content of described anion with respect to described furane resins active ingredient 100 weight portions is0.006～0.60 weight portion, and described self-curing making molds uses adhesive composition at 25 DEG CUnder pH be below 6.
2. self-curing making molds adhesive composition according to claim 1, wherein,
Cation in described ionic compound is for being selected from the periodic table of chemical element the 1st family, the 2nd family andMetal ion in the element of 12 families.
3. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
Anion in described ionic compound is for being selected from thiosulfuric acid ion, bisulfite ion and AsiaIn sulfate ion more than a kind.
4. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
The cation of described ionic compound is for being selected from Na ion, K ion, Mg ion, Ca ionAnd in Zn ion more than a kind.
5. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
Described ionic compound is for being selected from sodium hydrogensulfite, potassium bisulfite, sodium sulfite, sulfo-sulphurAcid sodium, potassium thiosulfate, magnesium thiosulfate, calcium thiosulfate, sodium tetrathionate and hydrosulfurous acidIn sodium more than a kind.
6. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
The content of described anion is 0.009 weight with respect to described furane resins active ingredient 100 weight portionsMore than amount part and below 0.50 weight portion.
7. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
The content of the anion of described ionic compound in adhesive composition, be 0.006 % by weight withUpper and below 0.54 % by weight.
8. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
The content of described ionic compound is more than 0.005 % by weight and 2.0 weights in adhesive compositionBelow amount %.
9. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
The pH of described furane resins is less than 7 at 25 DEG C.
10. self-curing making molds adhesive composition according to claim 1 and 2, itsIn,
Described furane resins are to be that acidic catalyst below 5.0 is synthesized into pKaResin.
11. self-curing making molds adhesive compositions according to claim 10, wherein,
Described acidic catalyst is for being selected from sulfuric acid, phosphoric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, dimethylbenzene sulphurAcid, Loprazolam, tartaric acid, citric acid, malic acid, glycolic, lactic acid, benzoic acid and formic acidIn more than a kind.
12. self-curing making molds adhesive compositions according to claim 1 and 2, itsIn,
The content of the free furfuryl alcohol in described furane resins is 20～98 % by weight.
13. self-curing making molds adhesive compositions according to claim 1 and 2, itsIn,
Furfuryl alcohol content in adhesive composition is more than 20 % by weight and below 98 % by weight.
14. self-curing making molds adhesive compositions according to claim 1 and 2, itsIn,
Moisture in described furane resins is more than 3.0 % by weight and below 30 % by weight.
15. self-curing making molds adhesive compositions according to claim 1 and 2, itsIn,
Described furane resins are that the content of furane resins active ingredient is more than 50 % by weight and 99 % by weightBelow.
16. self-curing making molds adhesive compositions according to claim 1 and 2, itsIn,
Moisture in adhesive composition is greater than 6.0 % by weight and is below 30.0 % by weight.
17. self-curing making molds adhesive compositions according to claim 1 and 2, itsIn,
The pH of adhesive composition is more than 2 and below 5.8 at 25 DEG C.
18. self-curing making molds adhesive compositions according to claim 1 and 2, itsIn,
Adhesive composition also contains and is selected from the two hydroxymethylfurans, 2 of 2,5-, 5-bi-methoxy methyl furanMutter, 2, the two ethoxyl methyl furans of 5-, 2-methylol-5-methoxy furans, 2-methylol-5-1 kind of above chemical combination in ethoxyl methyl furans and 2-methoxy-5-ethoxyl methyl furansThing.
19. 1 kinds of self-curing making molds compositions, it contains any one in claim 1～18Described self-curing is adhesive composition, fire resistance particle and acid curing agent for making molds.
Self-curing making molds adhesive composition in 20. claims 1～18 described in any oneThe purposes for Casting mold manufacturing.
The manufacture method of 21. 1 kinds of casting molds, it has:
By the adhesive composition for making molds of the self-curing described in any one in claim 1～18,Fire resistance particle and acid curing agent mix, and obtain the work of self-curing making molds compositionOrder, and
Make the operation of this mixture solidified.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011189265 | 2011-08-31 | ||
| JP2011-189265 | 2011-08-31 | ||
| PCT/JP2012/072159 WO2013031947A1 (en) | 2011-08-31 | 2012-08-31 | Adhesive agent composition for mold used in self-hardening molding and method for producing mold using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103764312A CN103764312A (en) | 2014-04-30 |
| CN103764312B true CN103764312B (en) | 2016-05-04 |
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| CN201280042567.4A Active CN103764312B (en) | 2011-08-31 | 2012-08-31 | Self-curing making molds is with adhesive composition and use the manufacture method of its casting mold |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9943903B2 (en) |
| EP (1) | EP2752258B1 (en) |
| JP (1) | JP5986457B2 (en) |
| KR (1) | KR101878534B1 (en) |
| CN (1) | CN103764312B (en) |
| WO (1) | WO2013031947A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5860530B2 (en) * | 2012-03-26 | 2016-02-16 | 積水化学工業株式会社 | Thermosetting furan resin composition and furan resin laminate using the same |
| JP6474322B2 (en) * | 2014-06-17 | 2019-02-27 | 花王株式会社 | Binder composition for mold making |
| JP6499852B2 (en) * | 2014-12-10 | 2019-04-10 | 花王株式会社 | Mold making kit |
| JP6736313B2 (en) * | 2016-03-02 | 2020-08-05 | 群栄化学工業株式会社 | Mold molding kit and method for manufacturing sand composition for mold molding |
| CN113231602B (en) * | 2018-08-01 | 2022-09-27 | 中国兵器工业第五九研究所 | High-performance composite casting mold for aluminum alloy casting |
| JP7329388B2 (en) * | 2018-09-11 | 2023-08-18 | 花王株式会社 | Binder composition for mold making |
| CN111185574B (en) * | 2020-03-13 | 2021-02-19 | 浙江浦江精宇铸造有限公司 | Lost foam casting process of nodular iron casting |
| TWI774165B (en) * | 2020-12-24 | 2022-08-11 | 金隆化學工業股份有限公司 | A method for binder and additive manufacturing. |
| CN113084081A (en) * | 2021-03-31 | 2021-07-09 | 苏州市兴业化工有限公司 | Rapid molding method of self-hardening furan resin for casting |
| JPWO2022254503A1 (en) * | 2021-05-31 | 2022-12-08 |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2752258A4 (en) | 2015-06-03 |
| WO2013031947A1 (en) | 2013-03-07 |
| US20140296372A1 (en) | 2014-10-02 |
| KR101878534B1 (en) | 2018-07-13 |
| US9943903B2 (en) | 2018-04-17 |
| EP2752258B1 (en) | 2017-10-04 |
| JP5986457B2 (en) | 2016-09-06 |
| JP2013063466A (en) | 2013-04-11 |
| KR20140059252A (en) | 2014-05-15 |
| EP2752258A1 (en) | 2014-07-09 |
| CN103764312A (en) | 2014-04-30 |
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